Nickel catalyst and method of preparing it



` R. IJLONGLEY, JR

NICKEL CATALYST AND METHOD OF PREPARING ITl Dec. 3o, 1947.

Filed May 11.., 1943 valu@ nomas APatented Dec. 30, 1947' Unir-'su STATES PATENT OFFICE NICKEL CATALYST AND BIETHOD `0F PREPARING IT Raymond I. Longley, Jr., Stamford, Conn., as-

sgnor to Air Reductiony Company, Incorporated, New York, N. Y., a corporation of New York Application May 11, 1943, Serial No. 486,513

This invention relates to thecatalytic hydrogenation of aldol to produce 1,3-butylene glycol and particularly to an improved nickel catalyst for use in the hydrogenation reaction and a method of preparing the catalyst.

The catalyst is especially. adapted for use in the continuous conversion of aldol by hydrogenation as described in the application of Frederick R. Balear, Ser. No. 479,771, led March 19, 1943, now U. S. Patent-No. 2,421,451, issued June 3, 1947. This applicationqdescribes a procedure in which a mixture of aldol and a reduction catalyst flows in the presence of hydrogen under elevated pressure through a succession of chambers, the reaction product being withdrawn continuously from the iinal chamber and separated from the catalyst. p

In such an operation conducted at a temperature preferably not exceeding 1009 C., andmore often as low as 75 C., it is essential that the catalyst be very active. Moreover, the catalyst s claims. (ci. 25a- 207) i The carrier upon which the nickel is deposited consists largely of silica and alumina with smaller proportions of magnesium, calcium and iron. titanium, sodium, potassium and manganese. A characteristic analysis after drying at 110 C. is:

S102 67.83 A1203 15.82 MgO 4.31 CaO 2.15

F6203 2.31 NazO-i-KzO 0.41 T102 0.35 Combined water and volatiles- 5.11

should be of such physical nature as to permit easy separation on standing from the reduction product. Nevertheless it must be suiiiciently finely divided to present adequate surface in order to maintain the desired rate of reduction.

It is the object o the present invention to provide a novel and active catalyst adapted foruse in the hydrogenation of aldol and a simple and eicient method of preparing such a 'catalyst.

Other objects and advantages of the invention will be apparent as it is better understood by reference to the following specification and accompanying drawing consisting of a 110W sheet indicating the preferred procedure in the prepa- As the preferred method of preparing the catalyst, pounds of nickel nitrateANi(NO-3)2.6H2O are dissolved in 2O gallons of hot water andthe resulting solution is added with stirring to a solution of 27.5 pounds of sodium carbonate dissolved in thirty gallons of hot water. 15 pounds of the carrier arethen added and the whole mass well agitated; The mixture may advantageously be kept hot duringthis agitation by the introduction of a current of steam. The sodium carbonate reacts with the nickel nitrate to form nickel carbonate-usually amixture ofthe pure carbonate and the basic carbonat'e'which deposits on the suspended carrier. The mixture is then iiltered and washed with hot water uutil substantially free from water soluble materials.

It also may contain small amounts of` The lter cake is then dried at 450 C., and is reduced by means of hydrogen at 450600 C. The reduction is conducted so. that the material is exposed to the reducing atmosphere for only a short period of time, as a rule not over 10 minutes and preferablyl about 1-5 minutes. The finished catalyst contains about 50% y by weight of nickel when the above proportions are used. While nickel nitrate is preferably used in the preparation of the catalyst, other nickel v salts such as the sulphate or chloridemay be used.

In the commercial preparation of the catalyst, the procedure indicated in the accompanying drawing may be followed. 5, 6 and 1 indicate respectively receptacles for nickel nitrate, sodium carbonate andthe carrier. These materials in the proper proportions are fed to the precipitator 8 which is supplied with steam as indicated yat 9. The resulting suspension is delivered through a pipe l and pump Il to a filter press l2, the filtrate being withdrawn through a pipe I3. -Water for washing is introduced through a pipe I4. The cake from the filter press is delivered to a hopper l and introduced by a conveyor I6 to a dryer i1, preferably of cylindrical type, which may be heated to the required temperature by combustible gas supplied to a burner I8. After drying, the material is delivered through a chute i9 to the reducing furnace 20, aiso preferably of the rotating cylindrical type, heated by combustible gas supplied to the burner 2|. Hydrogen as the reducing agent is supplied through a pipe 22 and is withdrawn through a head 23 and vent pipe 24. The reduced product is delivered to a receiver 25 which is supplied with an inert gas through a pipe 26 to prevent contact of the atmosphere with the finished catalyst. The catalyst may be withdrawn as re` quired and supplied to the reaction. The improved catalyst prepared in the manne described is remarkably active as is shown by the fact that when aldol was reduced at 100 C. under 300 pounds per square inch pressure of hydrogen and in the presence of 2% by weight of nickel mounted on the carrier, the percentage reduction of the aldol at the end of 30 and'60 minutes was respectively 85% and 98.6%. While the life of most nickel catalysts in this reaction is short, the catalyst described herein has shown very considerable improvement. It has been possible to use it successively for four separate reductions of aldol before the activity has been so impaired as to necessitate reviviiication. In each case the catalyst was separated from the 1,3-buty1ene glycol by settling and decantation.

Fresh. aldol was addedv and the I iydrogenation continued. The catalyst moreoverl lends itself readily to revivification in the manner described in the Balcar application above identified. The spent catalyst is Washed with water to free it from adhering glycol, dried, ground to disintegrate the cake formed by drying and then reduced under the conditions set forth above for the preparation of new catalyst. After such revivifcation, the catalyst was found to have reg'ained substantially all of its original activity.

Various changes may be made in the procedure and in the apparatus as described without departing from the invention or sacricing the advantages thereof.

I claim:

1. An improved aldol-hydrogenation catalyst consisting essentially of a nely-divided mineral acid-activated bentonite impregnated with about 50% by weight of the total catalyst of the nickel product derived by subjecting a nickel carbonate deposited thereon to a hydrogen-reducing atmosphere at a temperature of about 450 C. to 600 C. for a period from about 1 to 10 minutes. l

2. The method of preparing an aldol-hydrogenation catalyst comprising depositing a nickel carbonate on a. finely-divided acid-treated bentonite, and subjecting the bentonite with the i nickel carbonate deposited thereon to a hydrogenreducing atmosphere at a temperature of about 450 C. to 600 C. for a period of from about 1 tov 10 minutes to effect reduction of the nickel carbonate.

3. The method of preparing a. catalyst as set forth in claim. 2 in which the nickel carbonate is subjected to the hydrogen-reducing atmosphere for a` period of from 1 to 5 minutes.

' RAYMOND I. LONGLEY, JR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,040,233 Adkins May 12, 1936 1,282,296 Schwarcman Oct. 22, 1918 1,695,666 Schirmacker'et al. Dec. 18, 1928 1,775,366 Joseph Sept. 9, 1930 2,083,895 Connolly June 15, 1937 2,330,685 Connolly Sept. 28, 1943 2,309,263 Thomas Jan. 26, 1943 2,330,098 Watts Sept. 21, 1943 2,333,500 Welty Nov. 2, 1943 1,695,447 Woodruff et al. Dec. 18, 1928 1,427,037 Teichner Aug. 22, 1922 1,339,686 Boyce May 11, 1920 1,093,377 Boberg Apr. 14, 1914 2,365,029 Voorhies, Jr. Dec. 12, 1944 2,398,899 Teter Apr. 23, 1946 OTHER REFERENCES Dana, Text Book of Mineralogy, revised by Ford, 1922, pages` 578 and 579.

Berkman et al., Cata1ysis," Reinhold Pub. Co., N. Y., 1940, page 478.

U. S. Bureau of Mines Technical Paper 609, 1940, page 12. 

